Reaction product of propylene polymer and wax, graft copolymers derived from polypropylene polymer and wax, hot melt adhesive compositions including the same, and methods of using and making the same

ABSTRACT

A reaction product and hot melt adhesive compositions that include the reaction product are disclosed. The reaction product includes the reaction product of a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha-olefin copolymer, a first wax that includes at least one of polyethylene wax, Fischer Tropsch wax and paraffin wax, and a free radical initiator and has a viscosity of no greater than 12,000 centipoise at 177° C.

BACKGROUND

The invention relates to reacting propylene polymer and wax in thepresence of a free radical initiator.

Hot melt adhesive compositions are used in a variety of applicationsthat require bonding two substrates together including, packagingapplications (e.g., corrugated board and cardboard), nonwovenapplications (e.g., disposable articles), bookbinding, and footwearmanufacturing. A hot melt adhesive composition is generally applied in amolten state and forms a bond as it cools and solidifies. It isimportant that adhesives used in packaging applications exhibit goodbond strength over a wide temperature range and fast set times. It isoften difficult to achieve a hot melt adhesive composition that exhibitsgood bonding properties at both low and high temperatures.

Hot melt adhesive compositions that are formulated with amorphouspolypropylene polymers are useful in a variety of applications. Manyamorphous polypropylene polymers exhibit a long open time, are quitetacky immediately after solidifying from a molten state, and remaintacky for an undesirable period of time after solidifying. Theseproperties are undesirable for applications that require short opentimes and non-tacky properties after solidification.

SUMMARY

In one aspect the invention features a propylene-wax copolymer thatincludes the reaction product of components that include a first polymerthat includes at least one of polypropylene homopolymer andpolypropylene-alpha-olefin copolymer, a first wax that includes at leastone of polyethylene wax and Fischer Tropsch wax, and a free radicalinitiator, and that are free of an unsaturated compound that includes atleast one functional group and having a molecular weight no greater than1000 g/mole, the reaction product having a polydispersity index of nogreater than 5 and a viscosity of no greater than 12,000 centipoise at177° C.

In another aspect the invention features a propylene-wax copolymer thatincludes the reaction product of components that include a first polymerthat includes at least one of polypropylene homopolymer andpolypropylene-alpha-olefin copolymer, a first wax that includespolyethylene wax, and a free radical initiator, the reaction producthaving a number average molecular weight greater than 5000 g/mole, apolydispersity index no greater than 5, and a viscosity of no greaterthan 12,000 centipoise at 177° C. In one embodiment, the componentsfurther include an unsaturated compound that includes at least onefunctional group. In some embodiments, the unsaturated compound includesat least one of maleic acid, maleic anhydride, and fumaric acid.

In some aspects, the invention features a propylene-wax copolymer thatincludes the reaction product of components that include a first polymerhaving a polydispersity index of no greater than 5 and including atleast one of polypropylene homopolymer and polypropylene-alpha-olefincopolymer, a first wax that includes at least one of polyethylene wax,Fischer Tropsch wax, and paraffin wax, a free radical initiator, andthat are free of an unsaturated compound that includes at least onefunctional group and having a molecular weight no greater than 1000g/mole, the reaction product exhibiting a viscosity of no greater than12,000 centipoise at 177° C.

In other aspects, the invention features a method of making a graftcopolymer, the method including blending a first polymer and a first waxin the presence of a free radical initiator for a period of time andunder sufficient conditions to achieve a reaction product having apolydispersity index of no greater than 5, the first polymer includingat least one of polypropylene homopolymer and polypropylene-alpha-olefincopolymer, and the first wax including polyethylene wax.

In another aspect, the invention features a method of making a graftcopolymer includes blending a first polymer and a first wax in thepresence of a free radical initiator and in the absence of anunsaturated compound that includes at least one functional group and hasa molecular weight no greater than 1000 g/mole for a period of time andunder sufficient conditions to achieve a reaction product having apolydispersity index of no greater than 5, the first polymer includingat least one of polypropylene homopolymer and polypropylene-alpha-olefincopolymer, and the first wax including at least one of polyethylene waxand Fischer Tropsch wax.

In another aspect, the invention features a hot melt adhesivecomposition that includes a propylene-wax copolymer described herein. Insome embodiments, hot melt adhesive composition further includes atleast one of a tackifying agent, a plasticizer, and a wax.

In one aspect, the invention features a hot melt adhesive compositionthat includes a) a reaction product of components that include a firstpolymer that includes at least one of polypropylene homopolymer andpolypropylene-alpha-olefin copolymer, a first wax that includes at leastone of polyethylene wax and Fischer Tropsch wax, a free radicalinitiator, and that are free of an unsaturated compound that includes atleast one functional group and having a molecular weight no greater than1000 g/mole, the reaction product having a number average molecularweight greater than 0.5000 g/mole, a polydispersity index of no greaterthan 5, and a viscosity of no greater than 12,000 centipoise at 177° C.,and b) a tackifying agent. In one embodiment, the hot melt adhesivecomposition further includes a second wax. In another embodiment, thefirst polymer has a polydispersity index of less than 5. In someembodiments, first polymer has a polydispersity index of less than 4.5.In other embodiments, the reaction product has a polydispersity index ofno greater than 4.5. In another embodiment, the reaction product has apolydispersity index of no greater than 4.

In some embodiments, the first polymer includes a polypropylenehomopolymer.

In one embodiment, the first wax is a non-functionalized wax. In anotherembodiment, the first wax includes polyethylene wax and Fischer Tropschwax. In other embodiments, the second wax includes at least one ofpolyethylene wax, polypropylene wax, Fischer Tropsch wax, paraffin, andfunctionalized wax. In some embodiments, the second wax includes atleast one of maleated polypropylene wax and maleated polyethylene wax.

In one embodiment, the first polymer includes polypropylene homopolymerand the first wax includes polyethylene. In another embodiment, thefirst polymer includes polypropylene homopolymer and the first waxincludes a Fischer Tropsch wax.

In other embodiments, the hot melt adhesive compositions describedherein include from about 30% by weight to about 80% by weight of thereaction product, from about 1% by weight to about 40% by weight of thetackifying agent, and from about 1% by weight to about 35% by weight ofthe second wax. In another embodiment, the hot melt adhesivecompositions described herein include from about 35% by weight to about70% by weight of the reaction product, and from about 5% by weight toabout 35% by weight of the tackifying agent.

In some embodiments, the hot melt adhesive composition exhibits a fibertearing bond at −29° C. and at 60° C. In other embodiments, the hot meltadhesive composition exhibits at least about 50% fiber tear at −29° C.and at 60° C. In one embodiment, the hot melt adhesive compositionexhibits at least 80% fiber tear at 71° C.

In another embodiment, the hot melt adhesive composition exhibits aninitial Gardner color of no greater than 3.

In other embodiments, the hot melt adhesive composition exhibits achange in viscosity of no greater than 10% after aging for 96 hours at177° C.

In some embodiments, the hot melt adhesive composition is free ofgelling after aging for 96 hours at 177° C.

In one embodiment, the composition exhibits a set time of no greaterthan 10 seconds. In another embodiment, the composition exhibits a settime of no greater than 5 seconds.

In some embodiments, the composition exhibits an energy to break of atleast 0.15 Joules. In one embodiment, the composition exhibits a strainat break of at least about 100%. In other embodiments, the compositionexhibits an energy to break of at least 0.15 Joules and a strain atbreak of at least 100%. In another embodiment, the composition exhibitsa heat stress resistance of at least 60° C. In one embodiment, thecomposition exhibits an energy to break of at least 0.15 Joules and aheat stress resistance of at least 60° C.

In another embodiment, the composition exhibits an energy to break of atleast 0.15 Joules and a strain at break of at least 100%, and furtherincludes a second wax selected from the group consisting of polyethylenewax, polypropylene wax, Fischer Tropsch wax, paraffin, maleatedpolypropylene wax, and maleated polyethylene wax.

In other embodiments, the composition exhibits an energy to break of atleast 0.15 Joules and a heat stress resistance of at least 60° C., andfurther includes a second wax selected from the group consisting ofpolyethylene wax, polypropylene wax, Fischer Tropsch wax, paraffin,maleated polypropylene wax, and maleated polyethylene wax.

In another embodiment, the composition exhibits a tensile strength of atleast 1.38 MPa.

In one embodiment, wherein the composition includes at least 10% byweight tackifying agent and exhibits at least about 75% fiber tear at−29° C.

In other embodiments, the reaction products disclosed herein include thereaction product of the first polymer, the first wax, the free radicalinitiator, and an unsaturated compound that includes at least onefunctional group. In one embodiment, the unsaturated compound includesat least one of maleic acid, maleic anhydride, and fumaric acid.

In another embodiment, the reaction products disclosed herein includethe reaction product of the first polymer, the first wax, the first waxbeing a non-functionalized wax, the free radical initiator, and a secondwax, the second wax being a functionalized wax.

In some embodiments, the hot melt adhesive compositions described hereinfurther include a nucleating agent.

In another aspect, the invention features an article that includes afirst substrate, a hot melt adhesive composition disclosed herein, and asecond substrate bonded to the first substrate through the hot meltadhesive composition. In one embodiment, the first substrate includescardboard.

In other aspects, the invention features a method of using the hot meltadhesive compositions disclosed herein, the method including contactinga first substrate that includes fibers with a hot melt adhesivecomposition disclosed herein, and bonding a second substrate thatincludes fibers to the first substrate through the hot melt adhesivecomposition such that the hot melt adhesive composition forms a fibertearing bond to the first substrate in no greater than 10 seconds. Insome embodiments, the hot melt adhesive composition exhibits a fibertearing bond to the first substrate in no greater than 5 seconds.

In another aspect, the invention features a hot melt adhesivecomposition that includes a reaction product of components that includea first polymer that includes at least one of polypropylene homopolymerand polypropylene-alpha-olefin copolymer, a first wax that includes atleast one of polyethylene wax, Fischer Tropsch wax, and paraffin wax,and a free radical initiator, the reaction product having a viscosity at177° C. that is less than the viscosity of a blend of the components ofthe reaction product other than the free radical initiator, the reactionproduct having a number average molecular weight greater than 5000g/mole, a polydispersity index of no greater than 5, and a viscosity ofno greater than 12,000 centipoise at 177° C. In one embodiment, thereaction product has a viscosity at 177° C. that is at least 20% lessthan the viscosity at 177° C. of the blend of the components of thereaction product other than the free radical initiator. In someembodiments, the hot melt adhesive composition further includes atackifying agent.

In other aspects, the invention features a hot melt adhesive compositionthat includes a reaction product of a first polymer that includes atleast one of polypropylene homopolymer and polypropylene-alpha-olefincopolymer, a first non-functionalized wax that includes at least one ofpolyethylene wax, Fischer Tropsch wax, and paraffin wax, and a freeradical initiator, and a tackifying agent, the reaction productexhibiting a viscosity of no greater than 12,000 centipoise at 177° C.,and the hot melt adhesive composition exhibiting at least one of anenergy to break of at least 0.15 Joules, a tensile strength of at least3.28 MPa, and a heat stress resistance of at least 65° C.

In some aspects, the invention features a hot melt adhesive compositionthat includes the reaction product of components that include a firstpolymer having a polydispersity index of no greater than 5 and includingat least one of polypropylene homopolymer and polypropylene-alpha-olefincopolymer, a first wax that includes at least one of polyethylene wax,Fischer Tropsch wax, and paraffin wax, a free radical initiator, andbeing free of an unsaturated compound that includes at least onefunctional group and that has a molecular weight no greater than 1000g/mole, the reaction product exhibiting a viscosity of no greater than12,000 centipoise at 177° C.

In yet other aspects, the invention features a hot melt adhesivecomposition that includes the reaction product of a first polymer thatincludes at least one of polypropylene homopolymer andpolypropylene-alpha-olefin copolymer, a first wax that includespolyethylene wax, and a free radical initiator, the reaction producthaving a number average molecular weight greater than 5000 g/mole, apolydispersity index no greater than 5, and a viscosity of no greaterthan 12,000 centipoise at 177° C.

The hot melt adhesive exhibits good bond strength over a widetemperature range and good adhesion to packaging materials.

Other features and advantages will be apparent from the followingdescription of the preferred embodiments and from the claims.

GLOSSARY

In reference to the invention, these terms have the meanings set forthbelow:

The term “wax” means a polymer having crystallinity and a weight averagemolecular weight (Mw) less than 20,000 g/mole.

The term “non-functionalized wax” refers to a wax that is free of polarfunctional groups.

DETAILED DESCRIPTION Hot Melt Adhesive Composition

The hot melt adhesive composition includes a reaction product of apropylene polymer, a wax, and a free radical initiator. The hot meltadhesive composition exhibits a viscosity of no greater than about 5,000centipoise (cP), no greater than about 4,000 cP, no greater than about3,500 cP, no greater than about 3,000 cP, no greater than about 2,500cP, or even no greater than about 2,000 cP, at 177° C. The hot meltadhesive composition preferably forms a fiber tearing bond at −29° C.and at 60° C., and preferably exhibits at least about 40%, at leastabout 50%, at least about 75%, at least about 80%, at least about 90%,or even at least 100% fiber tear at −29° C. and at 60° C., at 65° C., at71° C., at 75° C., or even at 77° C.

The hot melt adhesive composition also exhibits a set time of no greaterthan 15 seconds, no greater than 10 seconds, no greater than 8.5seconds, no greater than 7 seconds, or even no greater than 5 seconds.

The hot melt adhesive composition preferably exhibits at least one of astrain at break of at least 10%, at least about 50%, at least about 75%,at least about 100%, or at least even about 120%, a tensile strength ofat least 1.38 megapascals (MPa) (200 pounds per square inch (psi)), atleast about 1.72 MPa (250 psi), at least about 2.07 MPa (300 psi), atleast about 2.41 MPa (350 psi), at least about 2.76 MPa (400 psi), atleast about 3.26 MPa (475 psi), at least about 3.45 MPa (500 psi) atleast 4.14 MPa (600 psi) or even at least 4.48 MPa (650 psi), and anenergy to break of at least 0.15 Joules (J), at least about 0.20 J, ofat least about 0.25 J, or even at least about 0.40 J.

The hot melt adhesive composition also preferably exhibits a heat stressresistance of at least 55° C., at least 60° C., at least 65° C., or evenat least 70° C.

The hot melt adhesive composition also preferably exhibits an initialGardner color of no greater than 5, no greater than 4, or even nogreater than 3, a Gardner color of no greater than 11 or even no greaterthan 7 after aging for 96 hours at 177° C., or even a change in Gardnercolor of no greater than 9, of no greater than 7, or even of no greaterthan 5 after aging for 96 hours at 177° C. The hot melt adhesivecomposition preferably is free of gelling after aging for 96 hours at177° C. and preferably exhibits a change in viscosity of no greater thanabout 20% or even no greater than about 10% after aging for 96 hours at177° C.

Reaction Product

The reaction product is derived from a propylene polymer that is atleast one of a polypropylene homopolymer and a propylene-alpha-olefincopolymer, a first wax that is at least one of polyethylene wax, FischerTropsch wax, and paraffin wax, and a free radical initiator. Thereaction product includes a copolymer that includes units of thepropylene polymer and units of the first wax, and optionally at leastone of the propylene polymer and the first wax.

The reaction product preferably has a polydispersity index (Mw/Mn) of nogreater than 5.5, no greater than about 5.0, no greater than about 4.5,no greater than about 4.0, or even no greater than about 3, and aviscosity of no greater than about 12,000 cP, no greater than about10,000 cP, no greater than about 5000 cP, no greater than about 4000 cP,no greater than about 3500 cP, no greater than about 3000 cP, or even nogreater than about 2500 cP, at 177° C. Useful reaction products exhibita number average molecular weight (Mn) of at least 5000 grams/mole(g/mole), at least about 5500 g/mole, at least about 6000 g/mole or evenat least about 6500 g/mole.

The reaction product can exhibit a viscosity that is less than theviscosity of a blend of the components from which the reaction productis derived (other than the free radical initiator). The reaction productcan exhibit a viscosity that is at least 10%, at least about 20%, atleast about 30%, at least about 40%, at least about 60%, at least about70%, or even at least about 80% less than the viscosity of the blendfrom which the reaction product is derived.

The reaction product can exhibit at least one of the properties of thehot melt adhesive composition. Alternatively or in addition, thereaction product can be formulated with other components to exhibit atleast one of the properties of the hot melt adhesive composition. Thereaction product preferably is present in the hot melt adhesivecomposition in an amount of about 100% by weight, at least 30% byweight, at least about 35% by weight, at least about 40% by weight, nogreater than 99% by weight, no greater than about 90% by weight, fromabout 30% by weight to about 80% by weight, from about 35% by weight toabout 70% by weight, or even from about 40% by weight to about 60% byweight.

Propylene Polymer

Useful propylene polymers from which the reaction product can be derivedhave a polydispersity index (Mw/Mn) of no greater than about 5, nogreater than about 4.5, no greater than about 4, or even no greater thanabout 3. The propylene polymer preferably exhibits a viscosity of nogreater than 20,000 cP, no greater than 15,000 cP, or even no greaterthan 10,000 cP, at 190° C.

Useful propylene polymers include, e.g., polypropylene homopolymers,copolymers (i.e., copolymers, terpolymers, and higher order polymers) ofpropylene and at least one alpha-olefin co-monomer, and combinationsthereof. Useful propylene copolymers are derived from propylene and atleast one alpha-olefin co-monomer (e.g., alpha-olefin monomers having atleast two carbon atoms, at least four carbon atoms, and combinations ofsuch monomers). Useful alpha-olefin monomers include, e.g., ethylene,butene, pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl-hexene-1,5-ethyl-1-nonene, and combinationsthereof. Suitable alpha-olefin co-monomers include mono-alpha olefins(i.e., one unsaturated double bond) and higher order olefins (e.g., adi-olefin, e.g., 1,9-decadiene). Specific examples of suitablepropylene-alpha-olefin copolymers include propylene-ethylene,propylene-butene, propylene-hexane, propylene-octene, and combinationsthereof.

The propylene polymer preferably includes at least 50 mole %, at leastabout 60 mole %, at least about 70 mole %, at least about 80 mole %, atleast about 90 mole %, at least about 95 mole %, or even from about 50mole % to about 100 mole % propylene.

The propylene polymer optionally includes at least 2 mole %, at leastabout 5 mole %, at least about 10 mole %, at least about 20 mole %, atleast about 30 mole %, no greater than about 50 mole %, or even fromabout 20 mole % to about 50 mole % of at least one alpha-olefinco-monomer.

Useful propylene polymers include metallocene-catalyzed propylenepolymers. Suitable propylene polymers are commercially available under avariety of trade designations including, e.g., the L-MODU series oftrade designations from Idemitsu Kosan Co., Ltd (Japan) including, e.g.,L-MODU 5400, 5600, and 5901, the VISTAMAXX series of trade designationsfrom ExxonMobil Chemical Company (Houston, Tex.) including, e.g.,VISTAMAXX 6202 and 2330, and the LICOCENE series of trade designationsfrom Clariant Int'l Ltd. (Muttenz, Switzerland) including, e.g.,LICOCENE PP 1602 TP and PP 2602 TP.

The reaction product preferably is formed from at least at least 60% byweight, at least 70% by weight, at least 80% by weight, from about 70%by weight to about 99% by weight, from about 80% by weight to about 95%by weight, or even from about 85% by weight to about 95% by weightpropylene polymer.

Wax

Useful waxes from which the reaction product can be derived include,e.g., polyethylene waxes (e.g., polyethylene homopolymers), FischerTropsch waxes, paraffin waxes, and combinations thereof, alone or infurther combination with polypropylene wax. The wax preferably isnon-functionalized.

Useful polyethylene waxes are commercially available under a variety oftrade designations including, e.g., the EPOLENE series of tradedesignations from Westlake Chemical Corporation (Houston, Tex.)including, e.g., EPOLENE N-21 and N-14 polyethylene waxes, the BARECOseries of trade designations from Baker Hughes Inc. (Sugar Land, Tex.)including, e.g., BARECO C4040 polyethylene wax, and the AC series oftrade designations from Honeywell Int'l Inc. (Morristown, N.J.)including, e.g., A-C 8 and A-C 9 polyethylene waxes.

Useful Fischer Tropsch waxes are commercially available under a varietyof trade designations including, e.g., the BARECO series of tradedesignations from Baker Hughes Inc. (Sugar Land, Tex.) including, e.g.,BARECO PX-100 and PX-105 Fischer Tropsch waxes, the SHELLWAX series oftrade designations from Shell Malaysia Ltd. (Kuala Lumpur, Malaysia)including, e.g., SHELLWAX SX100 and SX105 Fischer Tropsch waxes, theVESTOWAX series of trade designations from Evonik Industries AG(Germany) including, e.g., VESTOWAX 2050 Fischer Tropsch wax, and theSASOLWAX series of trade designations from Sasol Wax North AmericaCorporation (Hayward, Calif.) including, e.g., SASOLWAX H105, C80, H1,and H4 Fischer Tropsch waxes.

Useful paraffin waxes are available under a variety of tradedesignations including, e.g., PARVAN 1580 and 1520 paraffin waxes fromExxonMobil Chemical Company (Houston, Tex.).

Useful polypropylene waxes are commercially available under a variety oftrade designations including, e.g., EPOLENE N15 from Westlake ChemicalCorporation (Houston, Tex.), HONEYWELL AC1089 from Honeywell Int'l Inc.(Morristown, N.J.), and LICOCENE 6102 from Clariant Int'l Ltd. (Muttenz,Switzerland).

The reaction product preferably is formed from about 1% by weight toabout 40% by weight, from about 3% by weight to about 30% by weight,from about 5% by weight to about 25% by weight, or even from about 7% byweight to about 15% by weight wax.

Free Radical Initiator

Useful free-radical initiators include, e.g., peroxide-type compounds,azo-type compounds, and mixtures thereof. Examples of suitableperoxide-type compounds include diacyl peroxides, peroxy esters, peroxyketals, di-alkyl peroxides, and hydroperoxides, specifically hydrogenperoxide, benzoyl peroxide, decanoyl peroxide, lauroyl peroxide,succinic acid peroxide, cumene hydroperoxide, t-butylhydroperoxide,t-butyl peroxy acetate, 2,2-di(t-butyl peroxy) butane di-allyl peroxide,2,5-dimethyl-2,5-di(t-butyl peroxy) hexane, cumyl peroxide, di-t-amylperoxide, and combinations thereof. Suitable 2,5-dimethyl-2,5-di(t-butylperoxy) hexanes are commercially available from United InitiatorIncorporated (Elyria, Ohio).

Examples of suitable azo-type compounds include azobisisobutyronitrile(AIBN), 2,2′-azobis(N,N-dimethyleneisobutyramide)dihydrochloride (oneexample of which is commercially available under the VA-044 tradedesignation from Wako Chemical Co.), 2,2′-azobis(2,4-dimethylvaleronitrile) (one example of which is commercially available under theV-65 trade designation from Wako Chemical Co.), VAZO 642,2-azobis(isobutyronitrile) and VAZO 672,2′-azobis(2-methylbutyronitrile) both of which are commerciallyavailable from du Pont de Nemours and Company (Wilmington, Del.),1,1′-azobis(1-cyclohexane carbonitrile), acid-functional azo-typeinitiators e.g., 4,4′-azobis(4-cyanopentanoic acid), and combinationsthereof.

The reaction product preferably is formed from about 0.005% by weight toabout 10% by weight, from about 0.1% by weight to about 5% by weight, oreven from about 0.2% by weight to about 2% by weight free-radicalinitiator based on the weight of the propylene polymer.

Optional Functional Unsaturated Compound

The blend from which the reaction product is derived can be free of anunsaturated compound that includes at least one functional group (i.e.,a functional unsaturated compound) and that has a molecular weightgreater than 1000 g/mole. Alternatively, the reaction product optionallyis derived from an unsaturated compound, a functional unsaturatedcompound, and combinations thereof. Useful functional groups include,e.g., acids, anhydrides, esters, hydroxyl, amides, epoxy, andcombinations thereof. Useful functional unsaturated compounds include,e.g., unsaturated acids, polyacids, polyanhydrides, and combinationsthereof. Examples of suitable unsaturated acids include acrylic acid andmethacrylic acid. Examples of suitable unsaturated polyacids andunsaturated polyanhydrides include dicarboxylic acids and tricarboxylicacids including, e.g., acids and anhydrides of aliphatic dicarboxylicacids (e.g. maleic acid, maleic anhydride, and fumaric acid), andcombinations thereof.

The reaction product can be derived from 0% by weight to no greater thanabout 7% by weight, no greater than about 0.01% by weight, no greaterthan 0.001% by weight, from about 0.1% by weight to about 3% by weight,or even from about 0.1% by weight to about 2% by weight of a functionalunsaturated compound, where the % by weight is based on the weight ofthe reaction product.

Reaction Process

The reaction product preferably is prepared by combining the propylenepolymer, wax, and free radical initiator (and any optional components)to form a reaction mixture and reacting the same at an elevatedtemperature (e.g., from about 150° C. to about 250 CC, or even fromabout 175° C. to about 225° C.) under a blanket of inert gas (e.g.,nitrogen). The peroxide or agent is dispersed in the reaction mixtureand the temperature of the process is at least as high as the meltingpoint of the polymer. The temperature preferably is sufficiently farabove the melting point to obtain reasonably good agitation of thepolymer. Useful processing temperatures include from about 100° C. toabout 250° C., from about 150° C. to about 220° C., or even from about170° C. to about 190° C. The temperature of the process preferably isinitially from about 10° C. to about 100° C. above the softening pointof the polymer or polymer mixture to be treated. The reaction time mayvary from less than a minute to several hours depending on thetemperature used and the half-life of the free radical initiator beingused.

The process can be carried out using any suitable method including,e.g., continuous processes, semi-continuous processes, and batchprocesses. Suitable continuous processes include, e.g., processes thatuse extruders (e.g., single screw, twin screw, disk screw, reciprocatingsingle screw, and pin barrel single screw) and processes that use tandemextrusion techniques. Suitable batch processes include, e.g., processesthat utilize reaction vessels. Suitable reaction vessels include thosemade from glass or metal. For example, the reactions may be conducted inglass flasks, glass lined reactors, steel autoclaves, extruders,Brabender plastographs, and Banbury mixers. The reactions may beconducted in the presence of air or under inert gases such as nitrogen.Although not required, it is also possible to carry out the treatment inthe presence of an inert solvent such as benzene. Optionally a vacuum isapplied to remove impurities and volatile by-products of the reactionprocess.

Tackifying Agent

The hot melt adhesive composition optionally includes a tackifyingagent. Tackifying agents suitable for use in the adhesive compositionpreferably have Ring and Ball softening point of less than about 160°C., less than about 150° C., or even less than about 140° C. Suitableclasses of tackifying agents include, e.g., aromatic, aliphatic andcycloaliphatic hydrocarbon resins, mixed aromatic and aliphatic modifiedhydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, andhydrogenated versions thereof; terpenes, modified terpenes andhydrogenated versions thereof; natural rosins, modified rosins, rosinesters, and hydrogenated versions thereof; low molecular weightpolylactic acid; and combinations thereof. Examples of useful naturaland modified rosins include gum rosin, wood rosin, tall oil rosin,distilled rosin, hydrogenated rosin, dimerized rosin, and polymerizedrosin. Examples of useful rosin esters include e.g., glycerol esters ofpale wood rosin, glycerol esters of hydrogenated rosin, glycerol estersof polymerized rosin, pentaerythritol esters of natural and modifiedrosins including pentaerythritol esters of pale wood rosin,pentaerythritol esters of hydrogenated rosin, pentaerythritol esters oftall oil rosin, phenolic-modified pentaerythritol esters of rosin, andcombinations thereof. Examples of useful polyterpene resins includepolyterpene resins having a softening point, as determined by ASTMmethod E28-58T, of from about 10° C. to about 160° C., hydrogenatedpolyterpene resins, and copolymers and terpolymers of natural terpenes(e.g. styrene-terpene, alpha-methyl styrene-terpene and vinyltoluene-terpene), and combinations thereof. Examples of useful aliphaticand cycloaliphatic petroleum hydrocarbon resins include aliphatic andcycloaliphatic petroleum hydrocarbon resins having Ring and Ballsoftening points of from about 10° C. to 160° C., the hydrogenatedderivatives thereof, and combinations thereof. Suitable aliphatic andcycloaliphatic petroleum hydrocarbon resins include, e.g., branched,unbranched, and cyclic C5 resins, C9 resins, and C10 resins.

Useful tackifying agents are commercially available under a variety oftrade designations including, e.g., the ESCOREZ series of tradedesignations from ExxonMobil Chemical Company (Houston, Tex.) including,e.g., ESCOREZ 5400, ESCOREZ 5415, ESCOREZ 5600, ESCOREZ 5615, andESCOREZ 5690, the EASTOTAC series of trade designations from EastmanChemical (Kingsport, Tenn.) including, e.g., EASTOTAC H-100R, EASTOTACH-100L, EASTOTAC H 130W, and EASTOTAC H142, the WINGTACK series of tradedesignations from Cray Valley HSC (Exton, Pa.) including, e.g., WINGTACK86, WINGTACK EXTRA, and WINGTACK 95, the PICCOTAC series of tradedesignations from Eastman Chemical Company (Kingsport, Tenn.) including,e.g., PICCOTAC 8095, the ARKON series of trade designations from ArkawaEurope GmbH (Germany) including, e.g., ARKON P-125, and under theREGALITE series of trade designations from Eastman Chemical Companyincluding, e.g., REGALITE R1125.

The adhesive composition preferably includes no greater than about 50%by weight, no greater than about 40% by weight, no greater than about30% by weight, no greater than about 20% by weight, no greater thanabout 10% by weight, no greater than about 5% by weight, at least about1% by weight, at least about 15% by weight, at least about 20% byweight, from about 1% by weight to about 40% by weight, from about 5% byweight to about 35% by weight, or even from about 10% by weight to about35% by weight tackifying agent.

Other Components

The hot melt adhesive composition optionally includes a variety ofadditional components including, e.g., wax, antioxidants, stabilizers,additional polymers, plasticizers, oil (e.g., aliphatic napthenic oil,white oil, and combinations thereof), adhesion promoters, ultravioletlight stabilizers, rheology modifiers, biocides, corrosion inhibitors,dehydrators, colorants (e.g., pigments and dyes), fillers, surfactants,flame retardants, nucleating agents, and combinations thereof.

Classes of useful waxes include, e.g., functionalized waxes,non-functionalized waxes, and mixtures thereof. Useful functionalizedwaxes include, e.g., functionalized polyethylene wax (e.g., maleatedpolyethylene wax and oxidized polyethylene wax), functionalizedpolypropylene wax (e.g., maleated polypropylene wax and oxidizedpolypropylene wax), polar waxes, functionalized stearamide waxes (e.g.,hydroxystearamide, N-(2-hydroxy ethyl)-12-hydroxystearamide,N,N′-ethylene bis 12-hydroxystearamide, and 12-hydroxy stearic acid N,N′ethylene-bis stearamide), and combinations thereof. Usefulnon-functionalized waxes include, e.g., Fischer Tropsch waxes,polyolefin waxes (e.g., polypropylene waxes and polyethylene waxes),stearamide waxes, benzoate ester waxes, animal waxes, vegetable waxes,paraffin waxes, microcrystalline waxes, metallocene waxes, glycerinmonostearate, sorbitan monostearate, and combinations thereof.

Useful commercially available functionalized waxes include, e.g., A-C597P and A-C 596P maleated polypropylene wax, which are available fromHoneywell International Inc.

Useful commercially available non-functionalized waxes include the waxesset forth above in the discussion of waxes from which the reactionproduct is derived.

The additional wax, when present in the hot melt adhesive composition,is preferably present in an amount of at least 0.2% by weight, at least2% by weight, at least about 5% by weight, at least about 10% by weight,no greater than about 35% by weight, no greater than about 30% byweight, no greater than about 25% by weight, from about 5% by weight toabout 25% by weight, or even from about 5% by weight to about 20% byweight.

Useful antioxidants include, e.g., pentaerythritoltetrakis[3,(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],2,2′-methylene bis(4-methyl-6-tert-butylphenol), phosphites including,e.g., tris-(p-nonylphenyl)-phosphite (TNPP) andbis(2,4-di-tert-butylphenyl)4,4′-diphenylene-diphosphonite,di-stearyl-3,3′-thiodipropionate (DSTDP), and combinations thereof.Useful antioxidants are commercially available under a variety of tradedesignations including, e.g., the IRGANOX series of trade designationsincluding, e.g., IRGANOX 1010, IRGANOX 565, and IRGANOX 1076 hinderedphenolic antioxidants and IRGAFOS 168 phosphite antioxidant, all ofwhich are available from BASF Corporation (Florham Park, N.J.), andETHYL 702 4,4′-methylene bis(2,6-di-tert-butylphenol). When present, theadhesive composition preferably includes from about 0.1% by weight toabout 2% by weight antioxidant.

Useful additional polymers include, e.g., homopolymers, copolymers, andterpolymers, thermoplastic polymers including, e.g., polyolefins (e.g.,polyethylene, polypropylene, metallocene-catalyzed polyolefins, andcombinations thereof), elastomers including, e.g., elastomeric blockcopolymers (e.g., styrene-butadiene-styrene, styrene-isoprene-styrene,styrene-ethylene/butene-styrene, styrene-ethylene/propylene-styrene,metallocene-based elastomeric block copolymers, and combinationsthereof), and functionalized versions thereof, and combinations thereof.Examples of suitable commercially available polymers include, e.g.,EPOLENE C-15 branched polyethylene, and EPOLENE C-10 branchedpolyethylene, which are available from Westlake Chemical Corporation(Houston, Tex.).

The optional polymer, when present in the hot melt adhesive composition,is preferably present in an amount no greater than about 10% by weight,no greater than about 5% by weight, no greater than about 3% by weight,or even from about 1% by weight to about 4% by weight.

Useful nucleating agents include, e.g., polymeric nucleating agents,minerals, amides, aromatic organic compounds, phosphate ester salts,organic salts and combinations thereof. Examples of suitable nucleatingagents include polypropylene, polypropylene wax, polyethylene,polyethylene wax, polystyrene, poly(vinylcyclohexane), stearamides,anthraquinones, fatty acid amides, adipic acid, benzoic acid, benzoicacid salts, phosphate ester salts, sorbitols, kaolin, talc andcombinations thereof. The nucleating agent preferably increases the setspeed of at least one of the reaction product and the adhesivecomposition. Suitable nucleating agents are commercially available undera variety of trade designations including, e.g., N-15 polypropylene waxfrom Westlake Chemical Corporation (Houston, Tex.), and HYPERFORMHPN-68L disodium cis-endo-bicyclo(2.2.1) heptane-2-3-dicarboxylate fromMilliken Chemical (Spartanburg, S.C.).

Uses

The reaction product can be applied on or incorporated in a variety ofarticles including, e.g., films (e.g., polyolefin films (e.g.,polyethylene and polypropylene), polyester film, metalized polymer film,multi-layer film, and combinations thereof), fibers, substrates madefrom fibers (e.g., virgin fibers, recycled fibers, synthetic polymerfibers (e.g., nylon, rayon, polyesters, acrylics, polypropylenes,polyethylene, polyvinyl chloride, polyurethane), cellulose fibers (e.g.,natural cellulose fibers such as wood pulp), natural fibers (e.g.,cotton, silk and wool), and glass fibers, and combinations thereof),release liners, porous substrates, cellulose substrates, sheets (e.g.,paper, and fiber sheets), paper products, woven and nonwoven webs (e.g.,webs made from fibers (e.g., yarn, thread, filaments, microfibers, blownfibers, and spun fibers) perforated films, and combinations thereof),tape backings, and combinations thereof.

The hot melt adhesive composition is useful for bonding a variety ofsubstrates including, e.g., cardboard, coated cardboard, paperboard,fiber board, virgin and recycled kraft, high and low density kraft,chipboard, treated and coated kraft and chipboard, and corrugatedversions of the same, clay coated chipboard carton stock, composites,leather, polymer film (e.g., polyolefin films (e.g., polyethylene andpolypropylene), polyvinylidene chloride films, ethylene vinyl acetatefilms, polyester films, metalized polymer film, multi-layer film, andcombinations thereof), fibers and substrates made from fibers (e.g.,virgin fibers, recycled fibers, synthetic polymer fibers, cellulosefibers, and combinations thereof), release liners, porous substrates(e.g., woven webs, nonwoven webs, and perforated films), cellulosesubstrates, sheets (e.g., paper, and fiber sheets), paper products, tapebackings, and combinations thereof. Useful composites include, e.g.,chipboard laminated to metal foil (e.g., aluminum foil), whichoptionally can be laminated to at least one layer of polymer film,chipboard bonded to film, Kraft bonded to film (e.g., polyethylenefilm), and combinations thereof.

The hot melt adhesive composition is useful in bonding a first substrateto a second substrate in a variety of applications and constructionsincluding, e.g., packaging, bags, boxes, cartons, cases, trays,multi-wall bags, articles that include attachments (e.g., strawsattached to drink boxes), ream wrap, cigarettes (e.g., plug wrap),filters (e.g., pleated filters and filter frames), bookbinding,footwear, disposable absorbent articles (e.g., disposable diapers,sanitary napkins, medical dressings (e.g., wound care products),bandages, surgical pads, drapes, gowns, and meat-packing products),paper products including, e.g., paper towels (e.g., multiple usetowels), toilet paper, facial tissue, wipes, tissues, towels (e.g.,paper towels), sheets, mattress covers, and components of absorbentarticles including, e.g., an absorbent element, absorbent cores,impermeable layers (e.g., backsheets), tissue (e.g., wrapping tissue),acquisition layers and woven and nonwoven web layers (e.g., top sheets,absorbent tissue), and combinations thereof.

The hot melt adhesive composition is also useful in forming laminates ofporous substrates and polymer films such as those used in themanufacture of disposable articles including, e.g., medical drapes,medical gowns, sheets, feminine hygiene articles, diapers, adultincontinence articles, absorbent pads (e.g., for animals (e.g., petpads) and humans (e.g., bodies and corpses)), and combinations thereof.

The hot melt adhesive composition can be applied to a substrate in anyuseful form including, e.g., as fibers, as a coating (e.g., a continuouscoatings and discontinuous coatings (e.g., random, pattern, and array)),as a bead, as a film (e.g., a continuous films and discontinuous films),and combinations thereof, using any suitable application methodincluding, e.g., slot coating, spray coating (e.g., spiral spray, randomspraying, and random fiberization (e.g., melt blowing)), foaming,extrusion (e.g., applying a bead, fine line extrusion, single screwextrusion, and twin screw extrusion), wheel application, noncontactcoating, contacting coating, gravure, engraved roller, roll coating,transfer coating, screen printing, flexographic, and combinationsthereof.

The invention will now be described by way of the following examples.All parts, ratios, percents, and amounts stated in the Examples are byweight unless otherwise specified.

EXAMPLES Test Procedures

Test procedures used in the examples include the following. All ratiosand percentages are by weight unless otherwise indicated. The proceduresare conducted at room temperature (i.e., an ambient temperature of fromabout 20° C. to about 25° C.) unless otherwise specified.

Method for Determining Viscosity

Viscosity is determined in accordance with ASTM D-3236 entitled,“Standard Test Method for Apparent Viscosity of Hot Melt Adhesives andCoating Materials,” (Oct. 31, 1988) using a Brookfield ThermosetViscometer Model RVDV 2+ and an appropriate spindle. The results arereported in centipoise (“cP”).

Fiber Tear Test Method

The percentage fiber tear is the percentage of fiber that covers thearea of the adhesive after two substrates, which have been previouslybonded together through the adhesive, are separated by force. Thepercentage of fiber tear exhibited by an adhesive composition isdetermined as follows. A bead of the adhesive composition measuring15.24 cm (6 inch)×0.24 cm ( 3/32 inch) is applied to a first substrateof ROCKTENN 44 pound 87% virgin liner board, using a ROCKTENN bondsimulator at the specified application temperature. Two seconds afterthe bead of adhesive is applied to the first substrate, the bead ofadhesive is contacted with a second substrate of ROCKTENN 44 pound 87%virgin liner board, which is pressed against the adhesive and the firstsubstrate with a pressure of 0.21 MPa (30 pounds per square inch (psi))for a period of 2 seconds. The resulting constructions are thenconditioned at room temperature for at least 4 hours and thenconditioned at the specified test temperature for at least 12 hours. Thesubstrates of the construction are then separated from one another bypulling the two substrates apart from one another by hand. The surfaceof the adhesive composition is observed and the percent of the surfacearea of the adhesive composition that is covered by fibers is determinedand recorded. A minimum of five samples are prepared and tested for eachhot melt adhesive composition. The results are reported in % fiber tear.

Set Time Test Method

A bead of adhesive composition measuring 15.24 cm (6 inch)×0.24 cm (3/32 inch) is applied to a first substrate of ROCKTENN 44 pound 87%virgin liner board, using a ROCKTENN bond simulator at the specifiedapplication temperature. 0.2 seconds after the bead of adhesive isapplied to the first substrate, the bead of adhesive is contacted with asecond substrate of ROCKTENN 44 pound 87% virgin liner board, which ispressed against the adhesive and the first substrate with a pressure of0.21 Mpa (30 pounds per square inch (psi)) for a period of 0.2 seconds.A timer is started as the bead is applied to the first substrate. Whenthe timer is at 3 seconds, the now formed bond is pulled apart. If thebond results in less than 100% fiber failure, another bond is made andpulled after 3.5 seconds. In this manner, the amount of time that isallowed to elapse prior to pulling the bond is increased in 0.5 secondincrements until the set time is arrived upon. The set time is theshortest amount of time in which a pulled bond results in 100% fiberfailure. Once a set time is achieved, the test is repeated one more timeto confirm the result. If the bond gives 100% fiber failure at 3seconds, the set time is recorded as no greater than 3 seconds. Theresults are reported in seconds (s).

Heat Stress Resistance Test Method

Heat stress resistance is measured according to standard number IOPPT-3006 entitled, “Suggested Test Method for Determining the Heat StressResistance of Hot Melt Adhesives,” using a starting temperature of 130°F. (54.4° C.) and five bonded samples per adhesive. The pass temperaturefor each adhesive, which is defined as the maximum temperature at which80% of the samples remain bonded, is the heat stress resistance and isreported in degrees Celsius (° C.).

Tensile Test Method

Tensile properties are determined using ASTM D638 modified by the filmthickness and aging time. Films of each sample are created by using adraw down square, which is preheated at 350° F. (177° C.), with a cutout of 40 mils, which when cooled provides a sample film thickness of 25mils. Each sample is heated to 350° F. (177° C.), poured onto a Teflonboard, and quickly drawn down using the square. Once cooled, thethickness of each film is measured using a micrometer. The target filmthickness is 25 mils+/−5 mils, where 1 mil is equal to 0.001 inch.Tensile specimens are punched out of the film using a Type IV dog bonedie. The thickness of the film specimen is not to vary by greater than 1mil along the gauge length of a given specimen. Specimens are aged atroom temperature for at least 12 hours prior to testing. The specimensare run on an INSTRON 4502 at 23° C., 50% relative humidity, and 2inch/min extension rate. A calibrated 100 N INSTRON static load cell isused to quantify the force, and an INSTRON 2663-821 Advanced VideoExtensometer, calibrated using a custom calibration bar, measures thechange in the gage length. BLUE HILL 2 software is used for dataacquisition and analysis.

Strain at break is calculated according to the portion of ASTM D638pertaining to “percent elongation at break,” and is reported in percent(%).

Maximum tensile strength is calculated according to the portion of ASTMD638 pertaining to “tensile strength,” and is reported in megapascals(MPa).

Energy to break is calculated by integration of the stress-strain curve,and is reported in Joules (J).

Thermal Conditioning Procedure

A 200 gram (g) sample of hot melt composition is placed in a 400milliliter (ml) PYREX glass beaker and held at 350° F. (177° C.) forperiods of 24 hours, 48 hours, 72 hours, 96 hours, and 200 hours. Analiquot is removed from the sample for testing at each of theaforementioned time periods.

Gardner Color

A sample is conditioned according to the thermal conditioning procedureand then tested (in the molten state) to determine Gardner color bycomparing the color of the sample against the Gardner Color Standards asset forth in ASTM D-1544. The comparison is made using a Gardner DeltaComparator equipped with an Illuminator available from PacificScientific (Bethesda, Md.). The result is reported as the numbercorresponding to the Gardner Color Standard.

Method for Determining Molecular Weight

Molecular weights (Mn, Mw, and Mz) are determined using a Polymer LabsPL-GPC 220 High Temperature Size Exclusion Chromatograph (HT-SEC)operating at 160° C. with 1,2,4-trichlorobenzene (TCB) as the mobilephase. The system contains three PL-gel mixed B columns in series and isequipped with a Refractive Index (R1) detector. The SEC operates at aflow rate of 1.0 ml/min with an injection volume of 100 μL All HT-SECsamples are prepared with a concentration of 4.0 mg/ml. Molecularweights are calculated from the Mark-Houwink relation using knownpolystyrene standards. For polystyrene the Mark-Houwink parameters areK=0.000121 and α=0.707; for polypropylene the Mark-Houwink parametersare, K=0.000190 and α=0.725. The results are reported in grams per mole(g/mole).

General Method for Preparing Reaction Products of the Examples

The polymer and wax are combined and heated to a temperature of from175° C. to 180° C. with mixing. A peroxide, e.g., 92%2,5-dimethyl-2,5-di(tertbutylperoxy)hexane (United InitiatorIncorporated, Elyria, Ohio), is then added, under nitrogen atmosphere,to the molten polymer and wax mixture in 4 or 5 portions over a periodof from 30 minutes to 45 minutes with mixing. After addition of theperoxide, the mixture is further heated and stirred under nitrogen foranother 45 minutes to 60 minutes. Vacuum is then applied by pulling apressure of about 29 inches of mercury (Hg) for 30 minutes, and thereaction product is recovered.

Control C1

Control C1 was L-MODU S400 polypropylene (Idemitsu Kosan Co., Ltd,Japan).

Examples 1-7

The reaction products of Examples 1-7 were prepared by combining 90% byweight L-MODU S400 polypropylene (Idemitsu) and 10% by weight wax of thetype specified in Table 1 and heating the same to from 175° C. to 180°C., with mixing, to achieve a molten liquid. The molten liquid was thentreated with 92% 2,5-dimethyl-2,5-di(tertbutylperoxy)hexane (UnitedInitiator Incorporated, Elyria, Ohio), in the amount specified (in % byweight) in Table 1, under nitrogen atmosphere.

The reaction products of Examples 1-7 were tested according to theViscosity Test Method at 177° C., and the weight average molecularweight (Mw), number average molecular weight (Mn), and z averagemolecular weight (Mz) were determined according to the Method forDetermining Molecular Weight. The polydispersity index (PDI) wascalculated by dividing Mw by Mn. The results are reported in Table 1.

Control C2

Control C2 was LICOCENE 2602 propylene-ethylene copolymer (Clariant IntlLtd., Muttenz, Switzerland).

Examples 8 and 9

The reaction products of Examples 8 and 9 were prepared by combining 90%by weight LICOCENE 2602 propylene-ethylene copolymer and 10% by weightwax of the type specified in Table 1 and heating the same to from 175°C. to 180° C., with mixing, to achieve a molten liquid. The moltenliquid was then treated with 92%2,5-dimethyl-2,5-di(tertbutylperoxy)hexane (United InitiatorIncorporated), in the amount specified (in % by weight) in Table 1,under nitrogen atmosphere.

The reaction products of Examples 8 and 9 were tested according to theViscosity Test Method at 177° C., and the weight average molecularweight (Mw), number average molecular weight (Mn), and z averagemolecular weight (Mz) were determined according to the Method forDetermining Molecular Weight. The polydispersity index (PDI) wascalculated by dividing Mw by Mn. The results are reported in Table 1.

TABLE 1 Sample C1 C2 1 2 3 4 5 6 7 8 9 Wax Type NA NA N11 N14 N21 N21N21 PX105 PX105 N21 PX105 Peroxide (% by weight) 0 0 0.71 0.71 0.71 0.580.89 0.58 0.71 0.58 0.58 Viscosity at 177° C. (cp) 12,000 5125 2760 26102430 3270 2040 2300 1655 1980 1200 Mw (g/mole) 47,800 28,400 30,80030,400 29,500 32,100 29,000 31,900 27,000 28,700 25,300 Mn (g/mole)19,900 7570 8130 7210 10,200 10,600 9220 6770 6350 6390 5330 PDI 2.43.76 3.79 4.22 2.9 3.03 3.2 4.71 4.25 4.5 4.7 Mz (g/mole) 75,000 55,00053,100 50,900 48,600 52,600 48,800 58,200 46,700 50,600 46,600 NA = NotApplicable N11 = EPOLENE N11 polyethylene wax (Westlake ChemicalCorporation, Houston, Texas) N14 = EPOLENE N14 polyethylene wax(Westlake) N21 = EPOLENE N21 polyethylene wax (Westlake) PX105 = BARECOFischer Tropsch wax (Baker Hughes Inc., Sugar Land, Texas)

Controls C3 and C4 and Examples 10-18

A series of reaction products (C3, C4, and 10-18) were preparedaccording to the General Procedure for Preparing a Reaction Product withthe exception that the components and the amounts thereof (in % byweight) used to form the reaction product were as set forth in Table 2below.

The Mw, Mn, and Mz for C3 were determined to be 24200 g/mol, 4130 g/mol,and 51000 g/mol, respectively. The Mw, Mn, and Mz for C4 were determinedto be 21,800 g/mol, 4300 g/mol, and 45,000 g/mol, respectively.

The polydispersity index of C3 and C4 was determined to be 5.87 and5.07, respectively.

TABLE 2 Sample C3 C4 10 11 12 13 14 15 16 17 18 REXTAC 2765 95 95 0 0 00 0 0 0 0 0 AC1783 5 0 0 0 0 0 0 0 0 0 0 L-MODU S400 0 0 90 90 90 84 9071.2 0 90 90 LICOCENE 2602 0 0 0 0 0 0 0 0 90 0 0 EPOLENE N14 0 0 10 100 0 0 8.0 0 0 0 EPOLENE N21 0 5 0 0 10 0 0 17.3 10 0 0 EPOLENE N15 0 0 00 0 7 0 0 0 0 0 BARECO PX105 0 0 0 0 0 7 10 3.5 0 10 0 PARVAN 1580 0 0 00 0 0 0 0 0 0 10 DHBP peroxide 1.09 1.7 1.07 0.80 1.12 0.83 0.88 0.710.58 0.58 0.71 REXTAC 2765 = propylene butene copolymer (Rextac LLC,Odessa, Texas) AC1783 = A-C-X 1783 maleated linear low densitypolyethylene wax having an acid number of 4.5, a saponification value of6.2, a viscosity at 140° C. of 60 centipoise, a penetration value of 0.5dmm, a Mw of 8,650, a Mn of 1700, a Mz of 18,000, and a Mw/Mn of 5.08(Honeywell International Inc., Morristown, New Jersey). L-MODU S400 =Idemitsu Kosan Co., Ltd LICOCENE 2602 propylene-ethylene copolymerEPOLENE N14 = polyethylene wax EPOLENE N21 = polyethylene wax DHBP = 92%2,5-dimethyl-2,5-di(tertbutylperoxy)hexane (United InitiatorIncorporated, Elyria, Ohio) BARECO PX105 = Fischer Tropsch wax PARVAN1580 = paraffin wax (Exxon Mobil Chemical Company, Houston, Texas)

Controls C5-C7 and Examples 19-27

Hot melt adhesive compositions were prepared by mixing, at 177° C. forapproximately 20 minutes, the components in the amounts (in % by weight)set forth in Table 3. The row heading “Reaction Product” refers to thereaction products of Controls C3 and C4 and Examples 10-16 from Table 2.

The hot melt adhesive compositions of Controls C5-C7 and Examples 19-27were tested according to the Viscosity test method at 177° C., the FiberTear test method at test temperatures −28.9° C., −17.8° C., 4.4° C., 60°C., 65.6° C., and 71.1° C., and the Heat Stress Resistance test method,and for Energy to Break, Strain at Break, and Tensile Strength accordingto the Tensile test method. The results are set forth below in Table 3.

TABLE 3 Sample C5 C6 C7 19 20 21 22 23 24 25 26 27 Reaction Product C3C3 C4 10 11 12 13 14 15 16 17 18 Amount of Reaction Product 88.65 73.65100 58 68 68 73 73 72 68 68 58 EASTOTAC H130W 0 15 0 15 15 15 15 15 22.515 15 15 BARECO PX105 0 0 0 10 5 0 0 0 0 0 0 10 EPOLENE N21 8.37 8.37 010 10 12.5 10 10 0 12.5 10 10 EPOLENE N14 0 0 0 0 0 0 0 0 0 0 0 0EPOLENE N15 0 0 0 5 0 2.5 0 0 2.5 2.5 0 5.0 LICOCENE 6102 0 0 0 0 0 0 00 0 0 5 0 A-C596P 0 0 0 1 1 1 1 1 2 1 1 1 A-C597P 1.48 1.48 0 0 0 0 0 00 0 0 0 IRGANOX 1010 0.5 0.5 0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5IRGANOX 1076 0.5 0.5 0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 PropertiesViscosity at 177° C. (cP) 930 800 630 770 1220 1350 1340 1200 1320 11401330 680 Set Time (s) 7 3.4 9 <3 <3 <3 <3 3 3 <3 3.5 <3 Strain at Break(%) 42 83 27 96 163 151 166 153 394 97 160 72 Tensile Strength (MPa)1.29 0.96 1.83 4.92 5.61 3.45 3.5 3.74 3.83 4.67 4.54 4.87 Energy toBreak (J) 0.05 0.07 0.04 0.31 0.41 0.4 0.43 0.4 1.0 0.35 0.46 0.21 HeatStress Resistance (° C.) 60 57.2 <54.4 68 65.6 57.2 65.6 60 71.1 ND 62.857.2 Initial Gardner Color 3 3 2 3 2 2 2 ND 1 1 ND 1 Gardner Color afterND ND ND 6 ND ND ND ND ND ND 4 ND aging for 96 hours at 177° C. FiberTear −28.9° C. 95 40 18 78 94 91 82 81 95 79 83 0 −17.8° C. 88 11 16 5450 77 91 74 88 60 91 0    4.4° C. 100 49 43 87 76 94 82 94 96 78 91 2    60° C. ND ND 44 ND 100 100 100 ND ND 88 100 100   65.6° C. 83 94 1586 100 100 100 100 100 89 100 78   71.1° C. 74 92 35 79 100 100 100 10096 89 81 30 EASTOTAC H130W = Eastman Chemical (Kingsport, Tennessee)BARECO PX105 = Fischer Tropsch wax EPOLENE N21 = polyethylene waxEPOLENE N14 = polyethylene wax EPOLENE N15 = polyethylene wax A-C596P =maleated polypropylene wax (Honeywell International Inc., Morristown,New Jersey) A-C597P = maleated polypropylene wax (HoneywellInternational) IRGANOX 1010 = antioxidant (BASF Corporation, FlorhamPark, New Jersey) IRGANOX 1076 = antioxidant (BASF Corporation) ND = Notdetermined.

Viscosity Determination of Controls C1, C2 and C8-C11

The viscosity of the polymers of C1 and C2 and blends of 10% by weightpolymer and 10% by weight wax of the type specified in Table 4 weredetermined according to the viscosity test method using spindle 27 at177° C. The results are reported in centipoise (“cP”) in Table 4.

TABLE 4 Blend C1 C2 C8 C9 C10 C11 Polymer PP PE PP PP PP PP Wax NA NAN11 N14 N21 PX105 Viscosity at 177° C. (cP) 12000 5125 ND 7330 8940 7260NA = Not Applicable PP = MODU S400 polypropylene PE = LICOCENE 2602propylene-ethylene copolymer EPOLENE N21 = polyethylene wax EPOLENE N14= polyethylene wax EPOLENE N15 = polyethylene wax

Other embodiments are within the claims. All references referred toherein are incorporated herein to the extent they do not conflict.

What is claimed is:
 1. A propylene-wax copolymer comprising: thereaction product of components comprising a first polymer comprisingpolypropylene homopolymer, polypropylene-alpha-olefin copolymer, or acombination thereof, a first wax comprising polyethylene wax FischerTropsch wax, or a combination thereof, and a free radical initiator, andbeing free of an unsaturated compound that includes at least onefunctional group and has a molecular weight no greater than 1000 g/mole,the reaction product having a number average molecular weight greaterthan 5000 g/mole, a polydispersity index of no greater than 5, and aviscosity of no greater than 12,000 centipoise at 177° C.
 2. Apropylene-wax copolymer comprising: the reaction product of componentscomprising a first polymer comprising polypropylene homopolymer,polypropylene-alpha-olefin copolymer, or a combination thereof, a firstwax comprising polyethylene wax, and a free radical initiator, thereaction product having a number average molecular weight greater than5000 g/mole, a polydispersity index no greater than 5, and a viscosityof no greater than 12,000 centipoise at 177° C.
 3. A propylene-waxcopolymer comprising: the reaction product of components comprising afirst polymer having a polydispersity index of no greater than 5 andcomprising polypropylene homopolymer, polypropylene-alpha-olefincopolymer, or a combination thereof, a first wax comprising polyethylenewax, Fischer Tropsch wax, paraffin wax, or a combination thereof, a freeradical initiator, and being free of an unsaturated compound comprisingat least one functional group and having a molecular weight no greaterthan 1000 g/mole, the reaction product exhibiting a viscosity of nogreater than 12,000 centipoise at 177° C.
 4. The copolymer of claim 1,wherein the reaction product exhibits a set time of no greater than 10seconds.
 5. The copolymer of claim 1, wherein the reaction productexhibits a set time of no greater than 5 seconds.
 6. A compositioncomprising the copolymer of claim
 1. 7. A hot melt adhesive compositioncomprising the copolymer of claim
 1. 8. The hot melt adhesivecomposition of claim 7, wherein the hot melt adhesive compositionexhibits an initial Gardner color of no greater than
 3. 9. The hot meltadhesive composition of claim 7, further comprising tackifying agent,plasticizer, wax, or a combination thereof.
 10. The hot melt adhesivecomposition of claim 7, wherein the composition is free of gelling afteraging for 96 hours at 177° C.
 11. The hot melt adhesive composition ofclaim 7, wherein the composition exhibits an energy to break of at least0.15 Joules.
 12. The hot melt adhesive composition of claim 7, whereinthe composition exhibits a heat stress resistance of at least 60° C. 13.The hot melt adhesive composition of claim 7, wherein the compositionexhibits a tensile strength of at least 1.38 MPa.
 14. The hot meltadhesive composition of claim 7, wherein the composition exhibits astrain at break of at least about 100%.
 15. The hot melt adhesivecomposition of claim 7, wherein the composition exhibits an energy tobreak of at least 0.15 Joules and a strain at break of at least 100%.16. The hot melt adhesive composition of claim 7, wherein thecomposition exhibits an energy to break of at least 0.15 Joules and aheat stress resistance of at least 60° C.
 17. The hot melt adhesivecomposition of claim 7, wherein the composition exhibits an energy tobreak of at least 0.15 Joules and a strain at break of at least 100%,and further comprises a second wax selected from the group consisting ofpolyethylene wax, polypropylene wax, Fischer Tropsch wax, paraffin,maleated polypropylene wax, and maleated polyethylene wax.
 18. The hotmelt adhesive composition of claim 7, wherein the composition exhibitsan energy to break of at least 0.15 Joules and a heat stress resistanceof at least 60° C., and further comprises a second wax selected from thegroup consisting of polyethylene wax, polypropylene wax, Fischer Tropschwax, paraffin, maleated polypropylene wax, and maleated polyethylenewax.
 19. The hot melt adhesive composition of claim 7, wherein the hotmelt adhesive composition exhibits an energy to break of at least 0.15Joules, a tensile strength of at least 3.28 MPa, a heat stressresistance of at least 65° C., or a combination thereof.
 20. The hotmelt adhesive composition of claim 7 further comprising a nucleatingagent.
 21. The copolymer of claim 1, wherein the first wax comprises anon-functionalized wax, and the components further comprise a secondwax, the second wax comprising a functionalized wax.
 22. A method ofmaking a graft copolymer, the method comprising: blending a firstpolymer and a first wax in the presence of a free radical initiator fora period of time and under sufficient conditions to achieve a reactionproduct having a number average molecular weight greater than 5000g/mole and a polydispersity index of no greater than 5, the firstpolymer comprising polypropylene homopolymer, polypropylene-alpha-olefincopolymer, or a combination thereof, and the first wax comprisingpolyethylene wax.
 23. A method of making a graft copolymer, the methodcomprising: blending a first polymer and a first wax in the presence ofa free radical initiator and in the absence of an unsaturated compoundcomprising at least one functional group and having a molecular weightno greater than 1000 g/mole for a period of time and under sufficientconditions to achieve a reaction product having a number averagemolecular weight greater than 5000 g/mole and a polydispersity index ofno greater than 5, the first polymer comprising polypropylenehomopolymer, polypropylene-alpha-olefin copolymer, or a combinationthereof, and the first wax comprising polyethylene wax, paraffin wax,Fischer Tropsch wax, or a combination thereof.
 24. An articlecomprising: a first substrate; and a composition comprising thecopolymer of claim 1 disposed on the substrate.
 25. The article of claim24, wherein the first substrate comprises cardboard.
 26. Thepropylene-wax copolymer of claim 2, wherein the components furthercomprise an unsaturated compound that includes at least one functionalgroup.
 27. The propylene-wax copolymer of claim 26, wherein theunsaturated compound comprises maleic acid, maleic anhydride, fumaricacid, or a combination thereof.
 28. A hot melt adhesive compositioncomprising the copolymer of claim
 2. 29. A hot melt adhesive compositioncomprising the copolymer of claim
 3. 30. A propylene-wax copolymercomprising: a reaction product of components comprising a first polymercomprising polypropylene homopolymer, polypropylene-alpha-olefincopolymer, or a combination thereof, a first wax comprising polyethylenewax, Fischer Tropsch wax, or a combination thereof, and a free radicalinitiator, the reaction product having a viscosity at 177° C. that isless than the viscosity of a blend of the components of the reactionproduct other than the free radical initiator, the reaction producthaving a number average molecular weight greater than 5000 g/mole, apolydispersity index of no greater than 5, and a viscosity of no greaterthan 12,000 centipoise at 177° C.